氮硅取代的氮杂烯丙基锂、铁(Ⅱ)和钴(Ⅱ)的合成及结构(英文)

Synthesis and Structure of N-Silyl-Substituted the Lithium, Iron(Ⅱ) and Cobalt(Ⅱ) 1-Azaally Complexes

本文以[(Me2)NCH2C6H4CHSiMe2(NMe2)]Li(TMEDA)与叔丁腈为原料按1∶1加成得到氮杂烯丙基的锂化合物[{(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)Li(TMEDA)]即1。然后用乙醚或四氢呋喃作溶剂化合物1和二氯化亚铁或二氯化钴按2∶1反应得到氮杂烯丙基铁或钴的化合物分别为2和3。通式为M[{(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)]2(M=Fe(2),Co(3))。化合物1,2和3的结构分别用1H NMR,13C NMR,元素分析和X-射线单晶衍射技术进行了表征。晶体结构表明化合物2和3结构类似,都是以金属为对称中心的硅桥联的端基氮配位的氮杂烯丙基化合物。

The N-silyl-Ni-1-（2-（（dimethylamino）methyl）benzyl）-N,N,1,1-tetramethylsilanamiolithium 1-azaally com-pound [{（Me2）NCH2C6H4}CHC（tBu）NSiMe2（NMe2）Li（TMEDA）] （1） was synthesized by interaction of [（Me2）NCH2C6H4 CHSiMe2（NMe2）]Li（TMEDA） with one equivalent of tertbutyronitrile （tBuCN）. The derivative iron（Ⅱ） and cobalt（Ⅱ） compounds were produced by the treatment of 1 with FeCl2 or CoCl2 in tetrahydrofuran or diethylether at zero temperature, respectively, with the general formula M[{（Me2）NCH2C6H4}CHC（tBu）NSiMe2（NMe2）]2 （M=Fe （2）, Co （3））. The 1-azaally complexes 1, 2 and 3 were also characterized by X-ray single crystal diffraction and NMR analysis. Structural analyses of 2 and 3 reveal that their molecular structures are very similar. The structure of the centrosymmetric crystalline Fe （Ⅱ） or Co （Ⅱ） is unusually within the present series of homoleptic metal （Ⅱ） 1-azaallyls in that it is an κ1-enamido metal complex. CCDC： 771795, 1; 771796, 2; 771797, 3.